Ethers-of hydroxydihydronorpolycyclopentadienes



Patented Feb. 12, 1946 ETHERSOF HYDROXYDIHY DBONOBPOLY- CYCLOPENTADIENES Herman A. Bruson, Philadelphia, Pa assignor .to The Resinous Products & Chemical Company, Philadelphia, Pa., a corporation of Deb'- ware No Drawing. Application February 20, 1943, Serial No. 478,840

19 Claims. (or. 260-611) This invention deals with ethers of hydroxydihydronorpolycyclopentadienes and to a method for their preparation.

I have found that polycyclopentadienes having two double bonds per molecule react in the presence of an acidic condensing agent with organic compounds having at least One alcoholic hydroxyl group to form ethers which, during the reaction, undergo a rearrangement of the terminal endomethylene cycle of the reacting polycyclopentadiene. As a result, there are formed ethers of the corresponding hydroxydihydronorpolycyclopentadiene.

In spite of the fact that in the original polycyclopentadienes there are two apparently equivalent olefinlc linkages, only one of these enters into the ether reaction and rearrangement even with large excesses of reagents.

Thus, dicyclopentadlene reacts with ROE, an organic compound having at least one alcoholic hydroxyl group, as follows:

The addition-rearrangement product formed from a compound having at least one alcoholic hydroxyl group and dicyclopentadiene in the presence of an acidic condensing agent may be generically represented wherein C3H4 is a propenylene group which in conjunction with the adjoining carbon atoms forms a cyclopenteno group.

In an analogous manner, tricyclopentadiene reacts only-at the terminal endomethylene cycle with saturation oi the double bond occurring there and simultaneous rearrangement to give an ether of dihydronortricyclopentadiene. The reaction may be represented in the following way:

C i l u (acidic l H l H catalyst) CH CH (g ar n CH3 H 01H H:'C I E RO-Q wherein Ca'Hrhas the same significance as above.

In similar fashion, there may be depicted the reaction of tetracyclopentadlene or pentacyclopentadiene with organic compounds having one or more alcoholic hydroxyl groups. In the case of a polyhydric hydroxyl-containing compounds, one i or more molecules of a polycyclopentadiene may be reacted with each molecule of said compound. Thus, ethylene glycol, a dihydric alcohol, may react with one or two molecules of a polycyclopentadiene, as follows:

CH CH1 no cmcnlo on and 4 OH CH:

In the case of glycol as a typical dihydric a1- cohol, the addition-rearrangement product in which both hydroxyl groups react with dicyclo- Dentadiene has the formula:

c cn, ca 0n his... in

.ous polycyclopentadienes, and mixtures of such Mixtures of the higherpolycyclopentadienes. polycyclopentadienes with dicyclopentadiene are convenient for carrying out the reaction of this invention, since the dicyclo compounds serve as fluxes for the higher polycyclopentadienes and their derivatives. The ether of the hydroxydi hydronordicyclopentadiene may -be separated, from the ethers of the other hydroxydihydronorpolycyclopentadienes.

In practicingthis invention, it has been found that a wide variety of organic compounds containing one or more alcoholic hydroxyl groups may be employed. The hydroxyl group is preferably primary or secondary. Compounds 'containing a tertiary hydroxyl group may also be used, provided, however, that they are not readily dehydrated. Examples of useful reactants having tertiary hydroxyl groups are a-hydroXYiSO- butyric acid and its esters or acetone cyanohydrin.

The useful alcoholic hydroxyl-containing compounds may be aliphatic, arylaliphatic, cycloaliphatic, including terpenic, hydroaromatic, or heterocyclic, and may be saturated or unsaturated, straight or branched chained, or cyclic. It has also been established that the non-hydroxyl portion of the reacting hydroxyl-containing com- I pound may contain a wide variety of groups or substituents, for example, halogen, cyano, thiocyano, isothiocyano, nitro,l:eto or acyl, mercapto, acyloxy, aldehydo, alkoxy, aryloxy; ether or thioether linkages in general, carbalkoxy, or carboxy groups.

I It should be noted at this point that in the 19 case of compounds having carboxyl groups, ex- 'cess polycyclopentadiene is necessary, since esteriflcation of the free carboxyl group by addition and simultaneous rearrangement of the polycyclopentadiene group occurs in addition .to etheriflcation with the alcoholic hydroxyl group.

Ester' formation of polycyclopentadienes with acids is described in my co-pending application Serial No. 476,639, filed February 20, 1943. Other reactive groups may similarly cause additional reaction with the polycyclopentadienes having two oleflnic linkages with consequent or subsequent etherification.

From the above discussion, it will be evident that under the influence of acidic condensing agents polycyclopentadienes form others with a wide variety of alcoholic hydroxyl-containing compounds and that the new reaction is one of wide applicability. Hydroxyl-containing reactants of perhaps greatest interest belong to the general class of unsubstituted alcohols, whether monohydric or polyhydric, which are not dehydrated at 60 C. by sulfuric acid. There are, how- 'ever, other important types of reactants other than the' simple alcohols. Other important groups include hydroxy esters, hydroxy acids, hydroxy ketones, hydroxy lactones, hydroxy aldehydes, ether alcohols, cyanoalcohols, thiocyano alcohols, halohydrins, nitro alcohols, and polymeric hydroxyl-containing compounds, including 40 polyvinyl alcohol, polysaccharides, starches, cellulose, cellulose ethers, and the like.

Typical useful compounds are listed herewith:

Methanol, ethanol, propanol, isopropanol, nbutanol,;sec.-butanol, iso-butanol, the primary and various secondary isomeric amyl alcohols, nhexyl alcohol, a-ethyl butanol, 2-hexanol, n-heptanol, n-octanol, capryl alcohol, a-ethyl hexanol, decanol, 5-ethyl-nonanol-2, dodecyl alcohol, tetradecanol, 7-ethyl-2-methyl-undecanol-4, cetyl alcohol, 3,9-diethyl tridecanol-6, oleyl alcohol, noctadecanol, allyl alcohol, crotonyl alcohol, cinnamyl alcohol, geraniol, phenyl ethyl alcohol,

' .methoxy ethanol, ethoxy-ethanol, butoxyethanol,

ph'enoxyethanol, ethylene glycol, propylene glycol, butylene glycol-2,3, diethylene glycol, triethvylene glycol, polyethylene glycols, di-isopropyl'ene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monophenyl ether, cerol, .tris(hydroxymethyl) -nitromethane, glycerol monochlorohydrin, glycerol dichlorohydrin, glyceryl e-phenyl ether, glyceryl a, 'y-dimethyl ether, trimethylene glycol, triphenylcarbinol, tetramethylene glycol, decamethylene glycol- '1, 10, ethylene chlorohydrin, propylene chlorohydrin, propargyl alcohol, ethylene cyanohydrin, acetone. cyanohydrin, ZA-dihydroxy-2-methyl pentane, propylene cyanohydrin, lactonitrile, mandelonitrile, -pthi ocyanophenoxyethanol, 2-nitro-2-methyl-l-propanol, p-'

tert.-butyl phenoxy ethanol, o-cyclohexyl phenoxy ethanol, 2,4 -dichloro-phanoxy ethanol, p-

tert.-octyl vphenoxy ethanol, p-phenyl phenoxy ethanol, panaphthoxy ethanol, z-nitro-phenoxy ethanol, p-acetyl phenoxy ethanol, p-benzoyl .phenoxy ethanol, cyclohexanol, p-methyl cycloneed not be pure.

stance, technical alcohol mixtures such as are 2,ao 4,ssa I 3 hexanol, cyclopentanol, o-cyclohexyl cyclohexanol, p-tert.-amyl cyclohexanol, ii-hydroxydihydro-dicyclopentadiene, borneol, fenchol, cholesterol, ethyl glycolate, ethyl lactate, dimethyl tartrate, ethyl citrate, benzyl alcohol, 2-nitro-2- 5 methyl-1,3-propanediol, ethyl-l o-hydroxy steerate, tetrahydro furi'uryl alcohol, phenyl thioethanol, ceryl alcohol, 2-nitro-2-ethyl-13-propanediol, castor oil, hydrogenated castor oil, ethyl malate, sorbitol, dibutyl tartrate, glycerol a, -y-di- 1o phenyl ether, mannitol, ethylene glycol monobenzyl ether, ethylene bromohydrin, and many others. The hydroxyl-containing compound used There may be used. for inobtained as by-products from the synthetic production of methanol by the reaction of hydrogen and carbon monoxide and known as "higher alcohols from the methanol synthes These comprise branched-chained primary and secondary 2 fluoride and its coordination complexes with oxy- 39 genated compounds, such as ethers, as, for example, BF'sCaHrOCaI-Iv, carboxylic acids, as BF3.2CH3COOH, carboxylic esters, as

ketones such as BFs.CH2COCHs, BF3.2C4H9OH, and water, such as BFa.(HsO)r, where a: is one or two, sulfuric acid, its esters, as ethyl acid sulfate, aromatic sulfonic acids, as toluene sulionic acid, aliphatic sulfonic acids, as butyl sulfonic acid, acidic salts such as zinc chloride, acidic clays, such as that sold under the trade name of Tonsil," tetraphosphoric acid, etc. The last few catalysts are useful in special cases but give rather poor yields compared to the yields obtained with the preferred catalysts, which comprise sulfuric acid, boron trifiuoride, and their derivatives.

Sulfuric acid is of particular value in promoting reactions involving the lower primary aliphatic alcohols. It is generally of use in the case of other alcohols also which are not readily polymerized Or dehydrated by the presence oi. concentrated sulfuric acid.

The boron fluoride group of catalysts is one of considerable importance. As indicated, it comprises not only boron triiluoride but also its coordination complexes. 01 these. the complexes with ethers are of particular utility since they are soluble in the reaction mixtures and produce no troublesome by-products. Typical of these complexes are BF'3.C2H5OC2H5 and It is interesting and surprising to note that although boron trifluoride promotes polymerization of cyclopentadienes to resins in the absence of an alcohol, it promotes ether formation and rearrangement for the combination of polycyclopentadiene and alcoholic hydroxyl-containing compound.

The quantity of active catalyst employed may be varied over a wide range. Good results have beenobtained with as little as 2 per cent. of catalyst based on the weight of polycyclopentadiene tion is strongly exothermic.

3 alcohols, as

ing an alcoholic hydroxyl-containing compound and a polycyclopentadiene is readily carried out .in the presence of one or more acidic condensing agents. The reaction may be initiated by mixing the components and catalyst at room temperature, at temperatures even around 0 C. in some cases, or at elevated temperatures. While it is generally desirable to control the temperature at the start, the reaction may be carried to completion either by continuing the reaction for a long time or by raising the temperature to accelerate the reactions involved. Temperatures as high as C. to 200 C. may thus be used, the upper temperature being limited by the cracking tendency of the various polycyclopentadienes to revert to simpler forms including cyclopentadiene. The reaction range of about 50 C. to about 25 C. is generally the most useful and is to be preferred. The reaction may be performed under normal, reduced, or increased pressures.

In some cases where the hydroxyl-containing compound contains a negative group, as, for example, in the case of ethylene chlorhydrin, glycerol dichlorohydrin, or 2-nitrobutanol, the reac- Hence, it is desirable and often even necesessary to cool the reacting mixturein order to control the reaction,

5 moderating the violence thereof, and preventing polymerization and possible side reactions. The reaction may also be controlled by the rate of mixing the reactants and by the use of a solvent or diluent, such as a hydrocarbon solvent, including petroleum ethers or petroleum naphthas, or chlorinated solvents, including carbon tetrachlo-. ride, ethylene dichloride, chloroform, dichlorobenzene, or ethers, including dioxane, etc.

After the reaction has been carried to a desired point, the acidic condensing agent is removed, as by washing with water or neutralization. The reaction product may then be distilled in many cases or otherwise purified, as by treatment with decolorizing clay or carbon, stripping, extraction, etc.

The following examples illustrate this invention, it bein understood that the proportions,

, temperatures, and time can be varied over a wide range ,without departing from the spirit of the invention.

Example 1 move calcium sulfate and excess lime; and the The comprecipitate washed with methanol. bined filtrate and washings were evaporated on a steam bath under reduced pressure (30-35 mm.) to remove methanol and water. The residual oil, weighing 542 grams, was distilled under reduced The had the following probable structure:

It came over at 80 C./7 mm. as a colorless oil having a-pleasant, fruity odor. The yield was 458 grams, or 70% of theory, based on the dicyclopentadiene employed. It possessed the following constants: u 1.4961: 114 410082; boiling points 94-95 C./12 111111., 217..CJ757 mm.

Example 2 To a solution of 33 grams of 98% sulfuric acid in 200 grams of methanol, 66 grams of tricyclopentadiene was added. The mixture was stirred rapidly and boiled under reflux for one and onehalf hours at 70 C. Part of the methanol (130 grams) was then distilled off and the residual product heated for two and one-half hours longer under reflux at 80 C. The reaction product was poured into 500 cc. of hot water and the oil layer separated. The oil was diluted with an equal volume of toluene, washed twice with warm water, then shaken with three parts of calcium hydroxide, and filtered. Th filtrate was evaporated to remove the toluene. The residual oil (66 grams) was distilled under reduced pressure.

The methoxydihydronortricyclopentadiene distilled over at 130-142 C./2 mm. as a colorless oil in ayield of 50 grams. Upon redistillation, it boiled at 156-160 C./9 mm. and possessed the following constants: N 1.5318; d4" 1.0'760.

- Example 3 To 200 grams of ethanol cooled to 5 C.,. 100 grams of 98% sulfuric acid was-gradually introduced so that the temperature didnot exceed 20 C. To this solution, 132 grams of dicyclopentadiene was added. The mixture was stirred rapidly and boiled under reflux on a steam bath for three Example 4 The procedure described in Example 3 was carried out, using 100 grams of 98% sulfuric acid, 200 grams of isopropanol, and 132 rams of dicyclopentadiene. The mixture was stirred rapidly and heated under a. reflux condenser at 96-98 C. for three hours. The'product was worked up by washing, neutralizing the washed oil with lime, filtering and distilling the filtrate under reduced pressure.

The isopropoxydihydronordicyclopentadiene distilled over between 70 and 90 C./ 2 mm. as a faintly yellow oil in a yield of 8'7 grams. Upon redistillation, it boiled at 10'l1.10 C./12 mm. and formed a colorless liquid having a pleasant odor. It possessed the following constants: n 1.4897; d4 0.9845; boiling point, 234 C. at 763 mm.

2,894,582 pressure (7 mm. of Hg). The product obtained Example 5 To 116 grams of allyl alcohol cooled to 0 0., 25 grams of 98% sulfuric acid was gradually added so that the temperature of the resulting mixture did not exceed 5 C. The solution was allowed to come to room temperature and was then mixed with 132 grams of dicyclopentadiene. This mixture was stirred and slowly heated on a steam bath in a flask equipped with a reflux condenser. After the initial exothermal reaction causing temperatures up to 108 C. was over the mixture was stirred for three hours at -100 C.,' then poured into water and the oil layer separated. The oil was mixed with an equal volume of toluene, stirred with five parts of powdered lime, and filtered. The filtrate was distilled un- Theyield wa 106 parts. Upon redistillation, it

boiled at 117-119 C./12 mm. and possessed the following constants: a 1.5000; 414" 0.9960.

Example 6 (a) A. solution of 200 grams of n-butanol,

grams of 98% sulfuric acid, and 132 grams of dicyclopentadiene was prepared as described in Example 1 and heated at 95 C. under a reflux condenser for three hours." Th product was washed with water, the oil taken up in toluene, neutralized with sodium carbonate, and finally distilled under reduced pressure.

The product, consisting of 108 grams of nbutyloxydihydronordicyclopentadiene, was a colorless oil boiling at 100-110 C./2 mm. .Upon redistillation, it 'boiled at 128 130? C./12 mm. and possessed the following constants: a 1.4841;'d4 0.9680. p y

(b) Twenty-five grams of boron trifluoride diethyl ether complex (BFaciHmo) was dissolved in 111 grams of noutanol. The solution was mixed with 132 grams of dicyclopentadiene and heated at 95 C. for seven hours and stirred under a reflux condenser. The product was washed twice with water, neutralized with soda, and distilled under reduced pressure. The yield of n-butyloxydihydronordicyclopentadiene was 1'76 grams, or 85% of theory.

(c) A mixture of 100 grams of sec.-butanol, 25 grams of BF3.C4H10O, and 132 grams of d'icyclopentadiene was treated as described in (b) above.

The yield of sec.-butyloxydihydronordicyclopentadiene boiling at 1008-110" C./3 mm. was

135 grams. Upon redistillation, it boiled at 123"- 126 C./12 mm. and formed a colorless liquid possessing the following constants: 11. 1.4830; (24 0.9583. It has a pleasant, melon-like odor.

(b) A mixture of 100 grams of iso-butanol, 25 grams of BF3.C4H100, and 132 grams of dicyclopentadiene was heated for three hours at 95C. under reflux. The product was worked up as in (b) above. The isobutyloxydihydronordicyclopentadiene distilled at 123-125 C./12 .mm. as a colorless liquid of pleasant odor in a yield of 163 grams. It possessed the following constants: 11 1.4808; d4 0.9545.

Example 7 To grams of ethylene chlorohydrin cooled to 5 (2., there was gradually added 25 grams of 98% sulfuric acid while the reaction mixture was stirred and maintained at 15-18- C. After all of the chlorohydrin had been added,'the mixture was allowed to come to room temperature (28 C.) and stirred thereat for oneand threequarter hours. To the solution thus obtained, 132 grams of dicyclopentadiene was added and stirring was continued. A gradual exothermal reaction set in, during which the temperature rose to 75 C. Within a half hour. After the reaction had subsided, the mixture was stirred at 9095 C. for two and one-quarter hours. The product was washed with water, and the residual oil was taken up in toluene and made alkaline by the addition of excess calcium hydroxide. The product was filtered and the filtrate distilled under reduced pressure.

The chloroethoxydihydronordicyclopentadiene of the probable'formula:

on on, om l o \CH l H: i cm- L a momcmoon Example 11 Example 12 A mixture of 182 grams of fl-phenoxyethanol.

. 15 grams of 98% sulfuric acid, and 132 grams of distilled over at 125131 C./6 mm. as a pale yellow oil in a yield of 125 grams. Upon redistillation, it came over as a colorless oil boiling at 129- 131 C./7 mm. and possessing thejollowing constants: n 1.5085; c24 1.1090.

Examlple 8 The procedure described in Example 5 was applied to a mixture of 176 grams of isobutyl carbinol, 25 grams of 98% sulfuric acid, and 132 grams of dicyclopentadiene. The product (120 grams), consisting of isoamyloxydihydronordicyclopentadiene, was a colorles oil. boiling at 123- 127 C./6 mm.

Example 9 To a solution of 25 grams of 98% sulfuric acid in 180 grams of glycol monoethyl ether (Cellosolve) prepared at 15-20 0., there 'was added 132 grams of dicyclopentadiene. The mixture was stirred and heated for three hours at 9498 C. The resulting product was washed with water and the oil layer diluted with toluene, and treated with 5 grams of powdered lime. The solution was then filtered and distilled under reduced pressure. The 13-ethhxyethoxydihydronordicyclopentadiene of the probable formula:

to 71 grams of ethylene cyanohydrin. The above mixture was then heated with 132 grams of dicyclopentadiene with rapid stirring at 95C. for one hour. The product was washed with water,

' neutralized with lime, filtered and distilled under reduced pressure.

The ,8 cyanoethoxydihydronordicyclopenta diene distilled over at 140-144 C./ 2 mm. as a colorless oil in a yield of 45 grams."

dicylclopentadiene was reacted and worked up as described in Example 9.

The V phenoxyethoxydihydronordicyclopentadiene distilled at 180-185 C./2 mm. as a pale yellow oil in a'yield of grams. Upon redistillation, it came over at 178-l80 C./2 mm. as a colorless oil having the following constants: a 1.5431; (i4 1.086.

Example 13 (a) The precedure described in Example 11 was applied to a'mixture of 195 grams of n-octanol-l, 25 grams of 98% sulfuric acid, and 132 grams of dicyclopentadiene. The n-octyloxydihydrodicyclopentadiene obtained was a colorless oil boiling at 150-154 C./2 mm. and possessing the following constants: 12 1.4802; (14 0.9305.

(b) A mixture of 160 grams of octanol-2, 30 grams of boron trifluoride-diethyl ether complex (BFaC4I-I10O), and grams of. dicyclopentadiene was stirred and heated at 95 C. under a reflux condenser for three hours. The product was washed thoroughly with warm water, followed by a soda wash. then dried and distilled under reduced pressure. The secondary octyloxydihydronordicyclopentadiene distilled at C/2-3 mm. as a colorless liquid in a yield of 165 grams. Upon redistillation, it boiled at C./8 mm. and possessed the following constants: 11 1.4782; d4 0.9277.

Example 1 4 .and the acidity was completely destroyed by means of lime. The filtered product was distilled under reduced pressure. The tetrahydrofurfuryloxydihydronordicyclopentadiene of the probable formula:

distilled over at 140-145 C./2-3 mm. as a colorless oil in a yield of 101 grams. Upon redistillation, it boiled at 139-141 C./2 mm. and possessed the following constants: a 1.5042; (14" 1.057.

Example 15 To a rapidly stirred mixture of 129 grams of 1,3-dichloro-2-propanol and 132 grams of dicyclopentadiene heated to 60 0., there was added dropwise, during the course of twenty minutes, 25

grams of boron trifluoride-diethyl ether complex,

care being taken to moderate the exothermal reaction by means of a cooling bath so that the reaction temperature did. not exceed 65 C.

After all oi the catalyst had been added and the reaction had ceased, the mixture was stirred fortwo hours longer at 55-60 C., then washed with hot watenfollowed by a wash with soda solution and then with water. The dark viscous oil was dried in vacuo on a steam bath. The yield was 205 grams. Upon distillation under reduced pressure, the dichloropropoxydihydronordicyclopentadiene distilled at 150-160 C./3 mm.as a colorless oil. Upon redistillation, it boiled at 140- 142 C./2 mm. and possessed the following con- I stants: a 1.5187; 64 1.191..

Example 16 A mixture of 30 grams of boron trifluoride-diethyl ether complex (1315543100), 186 grams of technical grade n-dodecanol (Lorol"), and 132 grams of dicyclopentadiene was stirred and heated heated at 70-80 C. foine hour and was then poured into water. A da rk oil separated and was on a steam bath for-three and three-quarter hours at 95 to 100 C. with hot water, then with soda solution, dried, and distilled under reduced pressure. The product distilled at 180-200 C./2 mm. as a faintly yellow oil in a yield of 200 grams. Upon redistillation, the n-dodecyloxydihydronordicyclopentadiene (170 grams) came over at 184-185 C./2 mm. as a colorless oil possessing the following constants: n 1.4815; d4" 0.9166.

Example 17 tralized with alkali, washed, dried, and distilled The phenylethyloxydiunder reduced pressure. hydronordicyclopentadiene distilled at 166-180 C./2 mm. as a pale yellow oil in a yield of 144 grams. Upon redistillation, it came over at 160 C./2 mm. as a colorless oil having the following constants: a 1.5387; d4 1.041.

Example 18 A mixture of 132 grams oi dicyclopentadiene and 270 grams of n-octadecanol (technical product known as *Stenol") was heated to 60 0., and to the. clear melt grams oi lBFb.C3HsO-C:Hs

The product was washed was added. The mixture was stirred for four hours at 95 C. It was washed several times with hot water, then with hot. soda solution, and finally with boiling water. An oil was separated which wasdried in vacuo at 100 C. and cooled. whereupon the product (400 grams) solidified. Upon distillation under reducedpressure, this yielded as the main fraction-a cut boiling at 235- 245 C./2 mm. which solidified in the cold to a colorless, low melting, waxy solid. Analysis indicated the product to be mainly n-octadecyloxydihydronordicyclopentadiene together with a washed with hot water several times to remove i the boron fluoride and any unchanged nitromethyl propanol. The residual oil was dried in vacuo at C. The yield was 192 grams. Upon distillation in vacuo, the product, having the probable formula:

ELLL

distilled at 155-160 C./2 mm. as a colorless oil. Upon redistillation, it boiled at'152-155 C./2 mm. and possessed the following constants: a 1.4980; d4 1.093.

Example 20 Dicyclopentadiene (132 grams) was added to a solution of 25 grams of boron fluoride-diethyl ether complex in grams of glyceryl-L3-dimethyl ether. The mixture was stirred and heated at 932-95 C. for three hours. The solution was then washed with warm water, followed by a wash with dilute soda solution, and finally with water. The product was dried under a reduced pressure oi 30 mm. on-a steam bath. The yield was 210 grams of an oil residue. Upon redistillation of this oil in vacuo, a product was obtained boiling at -140 C./2 mm., consisting of a colorless oil, 1.3-dimethoxy-propoxy-2- dihydro-nordicyclopentadiene. Upon redistillation, it boiled at 162 C./12 mm. and possessed the following constants: a 1.4851; (14" 1.036.

Example 21 Dicyclopentadiene (132 grams) was added to a mixture of 118 grams or glycol monobutylether ("Butyl Cellosolve) and 25 grams of boron fluoride-diethyl ether. .The mixture was stirred and heated on a steam bath at 95 C. for three hours under a reflux condenser. The dark purple liquid was washed with warm water, then with soda solution, washed again, and dried under reduced pressure of 30 mm. on a steam bath. The residual oil, weighing 220 grams, was distilled under reduced pressure. hydronordicyclopentadiene distilled at 135-140 C.'/3 mm. as a colorless liquid. The yield was 177 grams. Upon redistillation, it boiled at 169- 172 C./12 mm. and possessed the following constants: a 1.4808; d4" 0.9806.

, Example 22 The butoxy-ethoxydL aseusa H .60 C. and stirred. rapidly under a reflux condenser, there was added gradually 25.:rams of boron iluoride-diethyl ether. The mixtur was held at 60-65C. for three hours. It was then washed with hot water several times, and finally washed with soda solution followed by a water wash. The oil was dried at 30 mm. pressure on a steam bath at 90-95 C. The residual oil weighing 232 grams, was then distilled under re duced pressure.

T h e benzyloxydihydronordicyclopentadiene distilled at 150-158 C./2 mm. as a colorless oil in a yield of 155 grams. Upon redistillation, it

boiled at 160-162 C./4 mm. and possessed thefollowing constants: 12,, 1.5461; d4" 1.058.

Emample 23 (a) A mixture of 62 grams of ethylene glycol (1 mol), 132 grams of dicyclopentadiene (1 mol), and 25 grams of BF3.C2H5OC2H5 was stirred and gradually heated to 95 C. under. a reflux condenser. After about fifteen minutes, an exothermal reaction set in which raised the temperature to 125 C. The mixture was then heated 152154 C./12 mm. and possessed the following constants: n 1.5105; (14 1.085.

A higher boiling fraction (boiling point, 210- 215 C./2 mm.) was also obtained as a pale yellow oil (43 grams). Analysis showed it to be the di-ether. Upon redistillation, it boiled at 208- 210 C./2 mm. and possessed the following con stants: 11 1.5263; 114 1.077; iodine No. 161 (theory 156).

(b) A mixture of 62 grams of ethylene glycol (1 mol) and 10 grams of 98% sulfuric acid was made up at -20 C. To this was added 264 grams of dieyclopentadiene (2 mols), and the mixture was stirred at 95-98 C. for three hours. The product was worked up as in (a) above, and yielded 39 grams of p-hydroxyethoxydihydronordicyclopentadiene and 111 grams of di-(dicyclopentenyl) ether of ethylene glycol boiling at 208- 210C. /2 mm.

Example 24 A mixture of 152 grams of benzyloxyethanol (Benzyl Cellosolve) and 132 grams of dicyclopentadiene was heated to 55 C. and stirred while 30 grams of boron fiuoride-diethyl ether complex (BF3.C4H10O) was added dropwise during ten minutes. The mixture was stirred thereafter for two hours at 60-70 C. and finally for two hours at 95 C. It was then washed, neutralized, and dried in vacuo at 90 C. The yield was 277 grams of crude product. Upon distillation under reduced pressure, the benzyloxyethoxydihydronordicyclopentadiene distilled at 188195 C./2 mm. as a colorless oil in a yield of 112 grams. Upon redistillation, it boiled at 184-188 C./2 mm. and possessed the following constants: 15 1.5549; c24 1.067.

Example 25 To a stirred solution of 132 grams of dicyclopentadiene and 100 grams of cyclohexanol at 60 C., there was added gradually 25 grams of BFs.diethyl ether complex. The mixture was stirred for one hour at 60 C. The temperature was then 7 nlseii to 75 C. and the mixture stirred thereat' ,for one and three-quarter hours. Finally, the

temperature was'raised to 95- 97 C. A slight exothermal reaction set in (temperature, 101) which soon subsided. Thereaction mixture was then stirred for two hours at 95-97 (L. The product was separated, washed, neutralized, and dried in vacuo at C. The yield was 200 grams of residual oil. Upon distillation of this oil in vacuo, the cyclohexyloxydihydronordicyclopen tadiene distilled at 130-140 C./2 mm. as a colorless oil. Upon redistillation, it boiled'at 163-166 C./12 mm. and possessed the following constants: u 1.5083; d4" 1.009.

Example 26 A mixture of 106 grams of diethylene glycol and 132 grams of dicyclopentadiene was stirred at 60 C. and 25 grams of boron trifluoride-diethyl ether complex was run in dropwise. The mixture was stirred for one hour at 60-70 C., then for two and one-half hours at 70-80 C., and finally for two hours at C. The product was then washed with hot water, followed by a soda wash and a final water wash, and was distilled under reduced pressure. The fraction boiling at 150-160 C./3 mm. was a colorless oil, weighing 102 grams and having the probable formula:

of the ldi-dicyclopentenyl ether of diethylene glycol, having the formula C10H13OCH2CH2OCH2CH2OC10H13 Upon redistillation, itboiled at 232-236 C./2 mm. and possessed the following constants: 'n 1.5190; d4 1.081.

Example 27 To a mixture of 102 grams of 2-ethyl butanol and 132 grams of dicyclopentadiene was gradually added, with stirring, 20 grams of boron fluoride-diethyl ether complex at 50 C. The mixture was then stirred for' thirty minutes at 60-75 and then heated to 95 C An exothermal reaction set in, during which the temperature rose to 110 C. After the evolution of heat had subsided, the mixture was stirred for one hour longer at 95 C., then washed, neutralized, dried, and distilled under reduced pressure. The product, 2 ethyl-butyldihydronordicyclopentadiene, distilled at 123-126 C./2 mm. as a colorless liquid in a yield of grams. Upon redistillation, it boiled at 152 C./ 12 mm. and possessed the following constants: 11. 1.4830; (14 0.9476.

Example 28 A mixture of 99 grams of tricyclopentadiene and 47 grams of 2-chloroallyl alcohol was stirred at 60 C. while 15 grams of boron fiuoride-diethyl ether complex was added dropwise during the course of ten minutes. The mixture was stirred thereafter at 65 C. for four hours. It was washed with hot water, and soda solution, dried and distilled in vacuo. The desired z-cmoroi distilled at 189-192 C./3 mm. as a thick pale yellow oil in a yield of 59 grams of pure product, having the following constants: 12 15409; d4 1.145.

Example 29 To a mixture of 92 grams of glycerol and 132 washed with hot water thoroughly and dried at 90 C. under reduced pressure. The residual oil,

ing constants: a 1.4966; d4 1.093.

grams of dicyclopentadiene stirred at 5560 C.,

there was added dropwise 25 grams of boron fluoride-diethyl ether complex. The temperature was then raised to 70 C. and held at 7080 C. forthree and one-half hours. The product was washed with hot water, soda solution, water again and distilled in vacuo. The mono-ether of glycerol of the probable structure:

HOCHz-CHOH-CHr-O-CH Example 30 A mixture of 51 grams of n-hexyl alcohol, 99 grams of tricyclopentadiene, and 15 grams of boron fiuoride-diethyl ether complex was stirred at 95 C. for three hours. The product was washed with hot water, neutralized with soda, dried, and

distilled in vacuo.

The n hexyloxydihydronortricyclopentadiene distilled at 180184 C./2 mm. as a pale yellow oil. The yield Was 45 grams. It possessed the following constants: n 1.5139; (24 1.011.

Example 31 A mixture of 81 grams of ethylene chlorohydrin, 198 grams of tricyclopentadiene, and 25 gram of BF3.C2H5OC2H5 was stirred at 60-65 for one and one-quarter hours, then at 75 for three hours. The product was washed, neutralized with soda, and distilled in vacuo.

The ,8-chloroethoxydihydronortricyclopentadiene distilled at 180185 C.'/3 mm. as a pale yellow, viscous oil in a yield of 85 grams.

Example 32 A mixture of 119 grams of 2-nitro-1-butanol and 132 grams of dicyclopentadiene was heated to 60 C. and stirred while 20 grams of was added dropwise' during twenty minutes. The exothermal reaction was controlled by cooling so that the temperature was held at 60"- C. throughout the addition period. The mixture was then held at C. for five hours longer. It was .(theory 212.5).

Example 33 A mixture of 136 grams of powdered pentaerythrite and 132 grams of dicyclopentadiene was rapidly stirred at 50 C. while 25 grams of boron fluoride-diethyl ether complex was added dropwise. The temperature gradually rose to 60 C. and was held at 60-70 C. for one and one-half hours. The almost solid resulting mass was stirred with boiling water to remove catalyst and unreacted pentaerythrite. This was repeated several times. The product was then dissolved in toluene, filtered, and the filtrate evaporated under reduced pressure. The residual pentaerythrite ether of nordicyclopentadiene was an amber-colored hard resin having a hydroxyl number of 103. It was produced in a yield of grams. It was soluble in linseed oil or inpetroleum naphtha.

Example 34 A mixture of 132 grams of ethyl-a-hydroxy-isobutyrate and 132 grams of dicyclopentadiene was stirred at 50 C., and 25 grams of was added dropwise. The mixture was then stirred at 50-60 C. for three and one-half hours. It was cooled, mixed with an equal volume of toluene, and washed thoroughly with water, soda solution, and finally with water. The toluene was evaporated 011 under reduced pressure on a steam bath. The residual oil was distilled in vacuo. The product having the probable formula:

Eaiample 35 A mixture consisting of 240 grams of methoxy ethoxyethanol constants: n 1.4905; (14 1.047.

Example 36 To a stirred mixture of 134 grams of glycerol monoacetate and 132 grams of dicyclopentadiene at 55 0., there was added dropwise 25 grams of boron trifluoride-diethyl ether complex. The

saponification number, 214

mixture was then heated at 80 C. for three and one-half hours. It was cooled, washed with cold water, then with sodium carbonate solution, and

again with cold water. The product was dried in Example 40 A mixture of 132 grams of dicyclopentadiene and 150 grams of hydroxydihydronordicyclopentadiene on on, CfiT l C. CH

H: i l ou H HOCH was heated to 70 C. and stirred while 15 grams of boron trifluoridediethyl ether complex was added dropwise. The mixture was then stirred for six hours at 70 C. It was worked up by washing, neutralizing, and distillin in vacuo.

there was gradually added grams of boron fiuoride-diethyl ether complex. The mixture was stirred for four and one-quarter hours thereafter at 60 C. It was then cooled, washed twice with cold Water, taken up in toluene, Washed with cold soda solution, then again with water, and the toluene evaporated in vacuum. The residual oil (203 grams) was distilled at 12l5-142 C./2 mm. as a colorless oil. Th yield was 106 grams. Upon redistillation, the cut boiling at 125-128 C./2 mm. possessed the following constants: 11 1.4823; (i4 1.050; saponification number, 219

(theory 224). Analysis indicated it to have the formula:

CHa-CHOC1uHla Example 38 A mixture of '76 grams of glycolic acid (1 mol) and 262 grams of dicyclopentadiene (2 mols) was stirred at 50 C. while grams of boron fluoridediethyl ether complex was added dropwise during the course of five minutes. The strongly exothermal reaction was cooled externally with ice, the reaction temperature finally reaching 90 C. The mixture Was stirred thereafter at 80 C. for three hours. It was cooled, mixed with an equal volume of toluene, and washed several times with water followed by soda solution, and then with water. The toluene layer was separated and evaporated to dryness in vacuo on a steam bath. The residual oil, Weighing 290 grams, was distilled in vacuo.

At 210-230 C./2 mm., a pale yellow oil (62 grams) distilled which consisted of a mixture of the hydroxydihydronordicyclopentadiene ester of glycolic acid, HOCH2COOC1oH13, and the ether thereof, namely, C1oH13-OCH2COOC10H13. At 230 C./2 mm., a pale yellow oil (48 grams) distilled which was essentially the pure ether of the glycolate, CroH13-OCH2COOC10H13.

Example 39 A mixture of 66 grams of dicyclopentadiene, 15 grams of BF'a-diethyl ether, and 107 grams of 7- ethyl 2 methylundecanol 4 (Tetradecanol"), was heated and stirred at 90 C. for five hours. The product was washed, neutralized, dried, and distilled in vacuo as described above. The tetradecyloxydihydronordicyclopentadiene boiled at 175-185 C./2 mm. Upon redistillation, it came over as a colorless oil, having a boiling point of 176179 C./2 mm. and possessing the following constants: n 1.4915; 114 0.9388.

The resulting di-(dihydronordicyclopentadiene) ether distilled at C./2 mm. as a faintly yellow, somewhat viscous, oil in a yield of 108 grams. Upon redistillation, it came over as a colorless liquid boiling at 185-188 C./3 mm. and having the following constants: 12 1.5372; d4 1.077; iodine number, 185 (theory, 180). The hydroxydihydronordicyclopentadiene used is a colorless liquid boiling at 240 C., obtainable by reacting dicyclopentadiene with aqueous sulfuric acid as described in co-pending application Serial No. 476,645, filed February 20, 1943.

Example 41 To a. stirred mixture of 53 grams of dicyclopentadiene and 56 grams of ,e-thiocyanoethoxyethanol at 60 C., there was added 10 grams of boron trifiuoride-diethyl ether complex. The mixture was stirred at 68-70 C. for five and one-half hours, then washed, neutralized with soda, washed again, and distilled in vacuo. The ,8 thiocyanoethoxyethoxydihydronordicyclopentadiene distilled at 200-210 C./3 mm. as a pale yellow oil. Upon redistillation, it boiled at 198 C./3 mm. and possessed the following constants: n 1.5251; d4. 0.9415. It is useful as an insecticide against flies, mosquitoes, and other soft-bodied insects.

Example 42 (a) A mixture of 85 grams of p-tert.-amylcyclohexanol, 66 grams of dicyclopentadiene, and 15 grams of BFs-diethyl ether complex was reacted at 90 C. for live and one-half hours. After being worked up as described above, the p-tert.-amylcyclohexyloxydihydronordicyclopentadiene was obtained as a colorless oil boiling at 178180 C./2 mm.

(b) In the same manner, 91 grams of ocyclo hexylcyclohexanol in place of the tert.-amylcyclohexanol above yielded o-cyclohexylcyclohexyloxydihydronordicyclopentadiene as a colorless oil boiling at 186-190 C./3 mm. and possessing the following constants: a 1.5313; d4 1.0435.

' tion, dried, and'distilled in vacuo.

Emmple 44 To a stirred solution of 104 grams of ethyl glycolate and 132 grams 01' dicyclopentadiene at 50 0., there was added dropwise 25 grams of boron triiiuoiide-diethyl ether complex. The mixture was stirred for four and one-half hours at 60 0., then cooled, washed with cold water, soda solupentenyl ether of ethyl glycolate of the probable formula-- distilled at 150-160 C./5 mm. as a pale yellow oil in a yield of 80 grams. Upon redistillation, it came over as a colorless oil boiling at 134-136 C./1.5 mm. and having the following constants:

The dicyclo- 11 1.4920; d4 1.0871; saponification number, a

240 (theory, 237); iodine number, 111' (theory.

Example 45 To a stirred solution of 85 grams of acetone cyanohydrin and 132 grams of dicyclopentadiene at 60 0., there was added gradually grams of boron trifluoride-diethyl ether complex. The mixture was stirred at 70 C. for six and onehalf hours. It was then washed with water, neutralized, dried, and distilled in vacuo. The cyanoisopropoxydihydronordicyclopentadiene distilled at 130-135 C./3 mm. Upon reclistillation, it came over at 110-112 C./1-2 mm. as a colorless liquid having the following properties: 11. 1.4870; iodine number of 118 (theory, 1 7), and containing 6.3% of nitrogen (theory 6.4% N).

Example 46 To a stirred suspension of 55 grams of powdered mannitol and 118 gramsof dicyclopentadiene heated to 60 0., there was gradually added 15 grams of boron trifiuoride-cliethylether complex. The exothermal reaction was controlled by cooling so that the temperature did not exceed 75 C. The mixture was stirred for one hour longer at 60 C. The solidified mass was then washed several times with hot water, and the dark resinous product dissolved in warm toluene. The toluene solution was washed with water, then with soda,

and finally evaporated in vacuo at 100 C. The

residue was a brittle dark resin, weighing 130 grams, which was soluble in petroleum naphtha.

Example 47 Five hundred grams of dicyclopentadiene was heated in a closed autoclave at 1(:l0-1'70v C. for seven hours. Thewhite pasty mass obtained, consisting of tricyclopentadiene, tetracyclopentadiene, and pentacyclopentadiene together with some unchanged dicyclopentadiene, was mixed at 65 C. with 200 grams of ethanol and 50 grams of BFa-diethyl eth'er complex. The mixture was stirred and heated for 18 hours at 90 C. The

product was, washed with hot water, taken up The ethyloxydihydronorpentacyclopentadiene remained behind in the still as a solid which could not be distilled in vacuo without decomposition.

Example 48 To a stirred mixture of 186 grams of castor 011 (0.2 mol) and 79.2 grams of dicyclopentadiene (0.6 mol), there was added 10 grams of boron' trifiuoride-diethyl ether complex. -The mixture was stirred at. 90 C. for five hours. The dark viscous mass was then washed twice with water,

then with dilute soda solution, and finally with water. It was then heated in vacuo at about 2 mm. pressure at 200 C. to remove moisture and traces of unchanged dicyclopentadiene. The residual product weighed 261 grams and consisted of a viscous dark oil which, in contrast to castor oil, was readily soluble in kerosene or in mineral,

oil and can be used as a hydraulic fluid component for brakes and recoil systems. Chemically, the" product is chiefly the tri-dihydronordicyclopentadienyl ether of ricinoleic triglyceride.

Example 49 A mixture of 52 grams of menthol, 44 grams of dicyc1opentadiene,, 49 grams ofethylene dichloride, and 15 grams of (C2H5)20.BF3 was stirred for five hours at 48-50 C. and then for two hours at 90 C. The reaction mixture was washed with 'water and with a solution of soda ash. It was then dried in vacuo and the solvent distilled ofl. The residual oil (92 grams) was then distilled under reduced pressure, and the fraction passing over at 167-170 C. at 3 mm. was collected as a water-white oil. identified as menthoxydihydronordicyclopentadiene, having the following constants: d4 0.9787; n 1.5028.

Example By the same procedure as that used above, an I equivalent amount of borneol was reacted in 4 place of the menthol. The resulting bomyl ether boiled at 166170 C./3 mm. and had the followin; constants: (14 1.0079; n 1.5100.

In the presence of acidic condensing agents,

polycyclopentadienes of the formula:

.ucts may be represented by the following configuration:

s *s of! c cfi on on, I 7 CH; l ir c on Roc This was wherein R is the organic residue of an alcoholic hydroxyl-containing compound and n a number from zero to a small integer.

By the process here disclosed, new ethers are obtained in an inexpensive manner. These possess properties fitting them for a great variety ofindustrial applications. Many of the new ethers are useful as solvents for resins and waxes. High boiling ethers are useful as plasticizers for natural and synthetic resins and elastomers, including synthetic rubbers, polyvinyl chloride, polyvinyl esters, polystyrene, polyacrylic esters, polymethacrylic esters, co-polymers of such materials, rubber hydrochloride, chlorinated rubber, nitrocellulose, cellulose acetate, ethyl cellulose, cellulose acetate-butyrate, etc. taining such groups as halogen, nitro, cyano, thiocyano, etc., possess insecticidal action to a marked degree. Some of the lower ethers have pleasant, flowery odors which recommend them for such uses as scenting soaps, cosmetics, and the like.

Since the ethers possess a double bond, they may be reacted with hydrogen, halogen, thiocyanogen and similar a ents to yield new compounds which are useful as solvents, hydraulic fluids, oil additives, insecticides, etc. The ethers also react with sulfuric acid to give water-soluble products useful as wetting and penetrating agents, emulsifiers, and detergents.

Although in the above examples practically pure polycyclopentadienes have been used, the process shown may also be applied to mixtures of hydrocarbons which contain or more of the polycyclopentadienes having two double bonds per molecule, such as are obtained in the thermal cracking of petroleum or in the manufacture of -water gas. The reaction of the polycyclopentadienes provides a new means for separating the components of mixtures of unsaturated hydrocarbons and gives new utility to such products.

I claim:

l. A method for preparing ethers of hydroxydihydronorpolycyclopentadiene having an ether group on one terminal cycle and an olefinic linkage in the opposite terminal cycle which comprises reacting by addition .and rearrangement in the presence of an acidic condensing agent a polycyclopentadiene having two double bonds and having one to four endomethylene cycles per molecule and an organic compound which has at least one alcoholic hydroxyl group at a tempera ture above about 0 C. and below the depolymerization temperature of the polycyclopentadiene.

2. A method for preparing ethers of hydroxy dihydronorpolycyclopentadiene having an ether group 'on one terminal cycle and an olefinic linkage in the opposite terminal cycle which comprises reacting by addition and rearrangement in the presence of sulfuric acid a polycyclopentadiene having two double bonds and having one to four endomethylene cycles per molecule and an organic compound which has at least one alcoholic hydroxyl group at a temperature above about 0 C. and below the depolymerization temperature of the polycyclopentadiene.

3. A method for preparing ethers of hydroxydihydronorpolycyclopentadiene having an ether group on one terminal cycle and an oleflnic linkage in the opposite terminal cycle which comprises reacting by addition and rearrangement in the presence of a boron trifluoride catalyst a polycyclopentadiene having two double bonds and having one to fourendomethylene cycles per Derivatives conmolecule and an organic compound which has at least one alcoholic hydroxyl group at a temperature above about 0 C. and below the depolymerization temperature of the polycyclopentadiene.

4. A method for preparing ethers of hydroxydihydronorpolycyclopentadiene having an ether group on one terminal cycle and an olefinic linka e in the opposite terminal cycle which comprises reacting by addition and rearrangement in the presence of an acidic condensing agent a polycyclopentadiene having two double bonds and one to four endomethylene cycles per molecule with an alcohol at a temperature above about 0 C. and below about 125 C.

5. A method for preparing ethers of hydroxydihydronorpolycyclopentadiene having an ether group on oneterminal cycle and an olefinic linkage in the opposite terminal cycle which com-' prises reacting by addition and rearrangement in the presence of a boron trifluoride catalyst a polycyclopentadiene having two double bonds and one to four endomethylene cycles per molecule with an alcohol at a temperature abov about 0 C. and below about 125 C. 6. A method for preparing ethers of hydroxydihydronorpolycyclopentadiene having an ether group on one terminal cycle and an olefinic linkage in the opposite terminal cycle which comprises reacting by addition and rearrangement in the presence of sulfuric acid a polycyclopentadiene having two double bonds and one to four endomethylene cycles per molecule with an alcohol at a temperature above about 0 C. and below about C.

7. A method for preparing ethers of hydroxydihydronordicyclopentadiene having a double bond in a terminal five-membered ring which comprises reacting by addition and rearrangement in the presence of an acidic condensing agent dicyclopentadiene and an organic compound which has at least one alcoholic hydroxyl group at a temperature above about 0 C. and below the cracking temperature of dicyclopentadiene.

8. A method for preparing ethers of hydroxydihydronortricyclopentadiene having a double bond in a terminal five-membered ring which comprises reacting by addition and rearrangement in the presence of an acidic condensing agent tricyclopentadiene having two double bonds and two endomethylene cycles per molecule and an organic compound which has at least one alcoholic hydroxyl group at a temperature above about. 0 C. and below the cracking temperature of the tricyclopentadiene.

9. A method for preparing ethers of hydroxydihydronordicyclopentadiene having a double bond in a terminal five-membered ring which comprises reacting by addition and rearrange-' ment in the presence of a boron trifluoride coordination complex of an oxygenated compound dicyclopentadiene and an alcohol at a temperature between about 0 C. and about 125 C.

10. A method for preparing ethers of hydroxydihydronordicyclopentadiene having a double bond in a terminal flve-membered ring which comprises reacting by addition and rearrangement in the presence oi boron trifiuoride coor-' dination complex of an oxygenated compound dicyclopentadiene and a primary aliphatic alcohol at a temperature between about 0 C. and about 125 C.

11. A method for preparing ethers of hydroxydihydroncrdicyclopentadiene having a double bond in a terminal ilve-membered ring which i comprises reacting by addition and rearrangement in the presence of a boron trifluoride coornation complex of an oxygenated compound dicyclopentadiene and a secondary aliphatic alcohol at a temperature between about 0 C. and

about 125 C.

12. ,A method for preparing ethers of hydrox'ydihydronortricyclopentadiene having a double bond in a terminal five-membered cycle which comprises reacting by addition and rearrangement in the presence of a boron trifluoride coornation complex of an oxygenated compound tricyclopentadiene having twodouble bonds and 1 two endomethylene cycles per molecule and an aliphatic'alcohol at a temperature above about 0 C. and below the cracking temperature of the tricyclopen'tadiene.

An dy ed, addition-rearrangement product of an crganiccompound having at least I one alcoholic hydroxyl group and a polycyclopentadiene having two double bonds, and one to four endomethylene cycles per molecule, said product being a dihydronorpolycyclopentadienyl ether of said organic compound.

14. An acid-catalyzed, addition-rearrangement l four endometnylene cycles per molecule, said,

product being a dihydronorpolycyclopentadienyl pentadiene having two double bonds and one to ether of said alcohol.

15. An acid-catalyzed, addition-rearrangement product of a primary aliphatic alcohol and di-. cyclopentadiene, said product being a dihydronordicyclopentadienyl ether. of said alcohol.

16. An acid-catalyzed, addition-rearrangement product of an organic compound having a sec-- ondary alcoholic hydroxyl group and -dicyclopentadiene, said product being a dihydronordicyclopentadienyl ether 01" said alcohol.

17. An acid-catalyzed, addition-rearrangement product 01' methyl alcohol and dicyclopentadiene,

said product being methyl dihydronordicyclo Dentadienyl ether.

18. An acid-catalyzed, addition-rearrangement product of butyl alcohol and dicylopentadiena' said product being butyl -dihydronordicyclo- I pentadienvl ether.

19. An acid-catalyzed, addition-rearrangement product of sec.-octyl alcohol and dicyclopenta-- .diene, said product being sec.-octy1 dihydronorg5 dicyclopentadienyl ether. v

product of an aliphatic alcohol and a polycyclo- HERMAN A. BRUSON. 

